20_ - P1: PCX/SRB JWDD052-20 P2: xxx JWDD052-Solomons-v3 20...

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P1: PCX/SRB P2: xxx Printer: Hamilton JWDD052-20 JWDD052-Solomons-v3 April 30, 2007 11:10 20 AMINES PREPARATION AND REACTIONS OF AMINES A. Preparation 1. Preparation via nucleophilic substitution reactions. NaN 3 , ethanol NH 3 RCH 2 NH 2 + (RCH 2 ) 2 NH + (RCH 2 ) 3 N (poor method) RCH 2 RCH 2 NH 2 N 3 Na/ethanol or LiAlH 4 RCH 2 Br RCH 2 N H H NH 2 NH 2 + RCH 2 NH 2 N N O O O O ΝΚ Ο Ο 2. Preparation through reduction of nitro compounds. HNO 3 NO 2 H 2 SO 4 (1) Fe, HCl H 2 , cat. or (2) OH NH 2 3. Preparation via reductive amination. Aldehyde or ketone NH 3 [H] CO R' R ' R NH 2 R CH R " NH 2 [H] R ' R ' R NHR " R CH R " R '" NH [H] R ' R ' RN R " R '" R CH 430
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P1: PCX/SRB P2: xxx Printer: Hamilton JWDD052-20 JWDD052-Solomons-v3 April 30, 2007 11:10 AMINES 431 4. Preparation of amines through reduction of amides, oximes, and nitriles. CN - H 2 Ni RCH 2 Br RCH 2 CN RCH 2 CH 2 NH 2 NH 2 OH Na/ethanol CO R ' R C R R ' CHNH 2 NOH R ' R (1) LiAlH 4 (2) H 2 O RNHR ' + R " CCl CNRR ' R " R " CH 2 NRR ' O O R (1) LiAlH 4 (2) H 2 O R ' CCl NH 2 NHCR ' R RNHCH 2 R ' O O + 5. Preparation through the Hofmann rearrangement of amides. SOCl 2 NH 3 RNH 2 + CO 2 2 - Br 2 /NaOH (NaOBr) RCOH O RCCl O RCNH 2 O B. Reaction of Amines 1. As a base or a nucleophile As a nucleophile in alkylation As a base NH O H + ++ HN H H 2 O + + N RCH 2 X + NC H 2 RX + As a nucleophile in acylation + NR C C l H NCR ( HCl) O O 2. With nitrous acid NH 2 RR R + alkenes, alcohols, and alkyl halides N 2 X HX 1 ° aliphatic (unstable) HONO + N 2
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P1: PCX/SRB P2: xxx Printer: Hamilton JWDD052-20 JWDD052-Solomons-v3 April 30, 2007 11:10 432 AMINES NH 2 1 ° aromatic 2 ° aliphatic X + HX (0–5 ° C) HONO R 2 NH R 2 NN N O HONO CuCl CuBr CuCN Δ HBF 4 Cu 2 O H 3 PO 2 KI ArCl + N 2 ArCN + N 2 ArI + N 2 N 2 + BF 3 ArF + ArN 2 + BF 4 ArOH N 2 + ArH N N NO H N 2 + ArBr + N 2 OH NR 2 Ar N NR 2 3 ° aliphatic 3 ° aromatic R 3 N R 2 N R 2 O + R 3 NH + X R 3 NX NaNO 2 2 ° aromatic ArNHR ArN R HONO HX HONO O + Ar Ar N 2 Ar Cu 2 + , H 2 O RN H 2 + ArSO 2 Cl R 2 NH + ArSO 2 Cl RNHSO 2 Ar R 2 NSO 2 Ar [RNSO 2 Ar] + H 2 O H 3 O + OH 3. With sulfonyl chlorides ( HCl) ( HCl) 1 ° amine 2 ° amine CC C C HO + 4. The Hofmann elimination + H N(CH 3 ) 3 (CH 3 ) 3 N + H 2 O heat +
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P1: PCX/SRB P2: xxx Printer: Hamilton JWDD052-20 JWDD052-Solomons-v3 April 30, 2007 11:10 AMINES 433 SOLUTIONS TO PROBLEMS 20.1 Dissolve both compounds in diethyl ether and extract with aqueous HCl. This procedure gives an ether layer that contains cyclohexane and an aqueous layer that contains hexy- laminium chloride. Cyclohexane may then be recovered from the ether layer by distillation. Hexylamine may be recovered from the aqueous layer by adding aqueous NaOH (to convert hexylaminium chloride to the hexylamine) and then by ether extraction and distillation. C 6 H 12 + C 6 H 13 NH 2 (in diethyl ether) C 6 H 12 (evaporate ether and distill) C 6 H 13 NH 2 (extract into ether and distill) H 3 O + Cl - /H 2 O aqueous layer ether layer OH - C 6 H 13 NH 3 Cl - + 20.2 We begin by dissolving the mixture in a water-immiscible organic solvent such as CH 2 Cl 2 or diethyl ether. Then, extractions with aqueous acids and bases allow us to separate the components.[Weseparate4-methylphenol( p
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20_ - P1: PCX/SRB JWDD052-20 P2: xxx JWDD052-Solomons-v3 20...

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